Catalytic metathesis has transformed chemical synthesis and offers exceptionally efficient pathways for the synthesis of commercially important chemicals, including but not limited to biologically active molecules, oleochemicals, renewables, fine chemicals, and polymeric materials. Organometallic catalysts based on ruthenium are used in many of such organic transformation reactions.
E.g., U.S. Pat. No. 7,723,255 B1 discloses a transition metal catalyst 1 having the following structure:
wherein:M comprises a transition metal such as Ru;R comprises an alkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxy carbonyl, alkylamino, alkylthio, alkylsulfonyl, or alkylsulfinyl; each optionally substituted with an alkyl, halogen, aryl or heteroaryl moiety; R1 and R2 each comprises, or together comprise, an electron withdrawing group;a, b, c and d each comprise a hydrogen or halogen atom or an alkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylamino, alkylthio, alkylsulfonyl or alkylsulfinyl group optionally substituted with an alkyl, halogen, aryl or heteroaryl moietyX is oxygen, sulfur, nitrogen or phosphorus; andY comprises an electron-donating heterocyclic carbene ligand.
Similar structures as in U.S. Pat. No. 7,723,255 B1 are disclosed in EP 1 313 559 B1.
U.S. Pat. No. 6,921,735 discloses ruthenium complexes bearing a 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene and styrenyl ether ligand.
U.S. Pat. No. 6,867,303 B2 discloses a compound of formula 2a,
whereinL1 is a neutral ligand;X and X′ are anionic ligands;R1 is C1-5 alkyl or C5-6 cycloalkyl;R2 is H, C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl or aryl;R3 is C1-6 alkyl, C1-6 alkoxy or aryl, wherein aryl is optionally substituted with C1-6 alkyl or C1-6 alkoxy;and n is 0, 1, 2 or 3.
U.S. Pat. No. 8,288,576 discloses a ruthenium catalyst having the following structure 2b:
wherein:X1 and X2 are the same or different and each selected from electron-withdrawing anionic ligands, wherein X1 and X2 may be linked to each other via carbon-carbon and/or carbon-heteroatom bonds;Y is a neutral two-electron donor selected from oxygen, sulfur, nitrogen or phosphorus;R is H, halogen atom, alkyl, alkoxy, aryl, aryloxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, heteroaryl, carboxyl, cyano, nitro, amido, amino, aminosulfonyl, N-heteroarylsulfonyl, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl, alkylthio, arylthio, or sulfonamido group;R1 and R2 are each H, Br, I, alkyl, alkoxy, aryl, aryloxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, carboxyl, amido, amino, heteroaryl, alkylthio, arylthio, or sulfonamido group;R3 is an alkyl, aryl, heteroaryl, alkylcarbonyl, arylcarbonyl, thiocarbonyl, or aminocarbonyl group;EWG is chloro or CO2Me; andL is an electron donating ligand, which may be linked to X1 via carbon-carbon and/or carbon-heteroatom bonds.
Similar compounds as in U.S. Pat. No. 8,049,025 are disclosed in U.S. Pat. No. 7,632,772.
WO 2014/201300 A1 discloses a ruthenium catalyst of formula 3
wherein the substituents R1, R2, R3, Rx, X, Y, and Z are broadly defined as specified therein.
WO 2017/055945 A1 discloses a ruthenium catalyst represented by the following formula
wherein:X1 and X2 are each independently an anionic ligand selected from halogen atoms, —CN, —SCN, —OR′, —SR′, —O(C═O)R′, —O(SO2)R′, and —OSi(R′)3 group, wherein R′ is C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C20 aryl, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy, or a halogen atom;Z is an atom selected from a group of O, S, NR′, wherein R′ is C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C20 aryl, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy, or a halogen atom;Ar is an aryl group substituted with hydrogen atoms or optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C5-C24 aryloxy, and C5-C20 heteroaryloxy group, or a halogen atom;R1 and R2, are each independently hydrogen atom, C1-C25 alkyl group, C1-C25 alkoxy group, C2-C25 alkenyl group, C1-C12 perfluoroalkyl, C5-C20 aryl, C5-C24 aryloxy, C5-C20 heteroaryloxy, or can be combined together to form substituted or unsubstituted C4-C10 cyclic or C4-C12 polycyclic system, can also be an ester (—COOR′), amide (—CONR′2), formyl (—CHO), ketone (—COR′), and hydroxamic (—CON(OR′)(R′)) group or a halogen atom, in which R′ is C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C20 aryl, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy, or a halogen atom;R3, R4, R5, R6 are each independently hydrogen atom, sulfoxide group (—S(O)R′), sulphonamide group (—SO2NR′2), phosphonate group (—P(O)(OR′)2), phosphinate group (—P(O)R′(OR′)), phosphoninum group (—P(OR′)2), phosphine group (—PR′2), nitro group (—NO2), nitroso group (—NO), carboxy group (—COOH), ester group (—COOR′), formyl group (—CHO), ketone group (—COR′), wherein R′ is C1-C5 alkyl, C1-C5 perfluoroalkyl, C5-C24 aryl, C7-C24 aralkyl, C5-C24 perfluoroaryl;wherein when R1 and R2 are —CH3 group, then at least one of R3, R4, R5, R6 substituents is not hydrogen atom;R7, R8, R9, and R10 are each independently hydrogen atom or C1-C25 alkyl group, R7 and/or R8 can be combined with R9 and/or R10 to form cyclic system, are also independently C1-C12 alkyl, C3-C12 cycloalkyl, C2-C12 alkenyl, C5-C20 aryl, C1-C5 perfluoroalkyl, C7-C24 aralkyl, and C5-C24 perfluoroaryl group, which are optionally substituted with at least one C1-C12 alkyl, C1-C12 perfluoroalkyl, C1-C12 alkoxy, C5-C24 aryloxy, C5-C20 heteroaryloxy, or a halogen atom.
U.S. Pat. No. 9,249,170 B2 discloses compounds of the following formula
wherein, independently for each occurrence,X is, independently for each occurrence, alkoxy or halo;R2 is, independently for each occurrence, alkyl;R3 is alkyl;R4 is alkyl, aryl, heteroaryl, aralkyl, or heteroaralkyl;or R3 and R4, taken together with the carbon atom to which they are attached, form a five-, six-, or ten-membered cycloalkyl or heterocyclyl ring;R5 is alkyl;R6 is H or alkyl, provided that (i) R5 and R6 are not the same, and (ii) R6 has fewer atoms than R5; andR7 is alkyl;or a compound of formula
wherein, independently for each occurrence,X is, independently for each occurrence, alkoxy or halo;R2 is, independently for each occurrence, alkyl;R3 is alkyl;R4 is alkyl, aryl, heteroaryl, aralkyl, or heteroaralkyl;or R3 and R4, taken together with the carbon atom to which they are attached, form a five-, six-, or ten-membered cycloalkyl or heterocyclyl ring;R5 is, independently for each occurrence, alkyl; andR7 is alkyl;or a compound of formula
wherein, independently for each occurrence,X is, independently for each occurrence, alkoxy or halo;R2 is alkyl;R3 is alkyl;R5 is, independently for each occurrence, alkyl;R7 is alkyl; andR8 is aryl or heteroaryl;or a compound of formula
wherein, independently for each occurrence,X is, independently for each occurrence, alkoxy or halo;R2 is alkyl;R3 is alkyl;R5 is, independently for each occurrence, alkyl;R7 is alkyl; andR9 is C2-C6 alkyl;or R3 and R9, taken together with the carbon atom to which they are attached, form a five-, or ten-membered cycloalkyl or heterocyclyl ring.